Umeå University's logo

umu.sePublications
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Valorization of biomass byproducts: the potential of chitin and lignin through solid catalysts
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2025 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Valorisering av biomassabiprodukter : potentialen hos kitin och lignin från fasta katalysatorers perspektiv (Swedish)
Abstract [en]

This research explores the potential of abundant biopolymers, specifically chitin and lignin, found in biomass byproducts to address environmental and energy challenges.

Chitin, commonly found in crustacean shells, can be deacetylated to produce chitosan, a versatile material with various industrial applications. Traditional chitosan production is energy-intensive and uses corrosive reagents.  In order to improve the process, Paper I introduces a ‘greener’ method, using the ionic liquid [Emim][OAc] for chitin pretreatment, followed by microwave-assisted deacetylation in aqueous NaOH or [TBA][OH] solutions. The pretreatment effectively reduces the chitin crystallinity, improving its reactivity for achieving up to 85% deacetylation in 1-2 hours. Both [Emim][OAc] and [TBA][OH] are regenerated (97% and 83%, respectively), offering a more sustainable chitosan production method, which can serve as a substrate for e.g. catalysts in industry. Paper II investigates the adsorption and catalytic reduction of phenol red dye using Ag-loaded chitosan catalysts. These catalysts display excellent activity across a broad pH range (4–11), with efficient adsorption at near-neutral pH (6.4) and room temperature. After five recycling cycles, the catalysts maintain structural stability, with only a 0.2% loss of Ag, demonstrating their potential for wastewater treatment.

Lignin, an abundant but underutilized polymer in wood biomass, is typically burned for heat. Recent interest has focused on converting lignin into valuable products like jet-fuel range hydrocarbons and fine chemicals. The challenge is selectively breaking C–O and C–C bonds in lignin while maintaining catalyst stability. Paper III explores C–O cleavage in lignin models using multifunctional Ru/NbOPO4/TiO2 catalysts, achieving high yields of hydrocarbons (86.9–100%) under mild conditions. Paper IV investigates both C–O and C–C cleavage with Ru/NbOPO4 catalysts, producing >99% conversion in model compounds with high yield of hydrocarbons. The catalysts’ performance is driven by the tunable synergy between Lewis and Brønsted acid sites of niobium phosphate and the hydrogen activation role of Ru.

This interdisciplinary research advances biopolymer chemistry and catalysis, offering sustainable solutions for environmental and energy challenges by maximizing biomass byproducts and providing eco-friendly alternatives in wastewater treatment and renewable energy.

Abstract [sv]

Denna forskning undersöker potentialen hos två viktiga biopolymerer, specifikt kitin och lignin, som finns i biprodukter från biomassa, för att möta miljö- och energirelaterade utmaningar. 

Kitin, som vanligen återfinns i kräftdjurskal, kan deacetylseras för att producera kitosan, ett mångsidigt material med olika industriella tillämpningar. Traditionell kitosanproduktion är energikrävande och använder korrosiva reagenser. För att förbättra denna process introducerar Paper I en ’grönare’ metod, där den joniska vätskan [Emim][OAc] används för förbehandling av kitin, följt av mikrovågshjälpt deacetylation i vattenlösningar av NaOH eller [TBA][OH]. Förbehandlingen reducerar effektivt kitinets kristallinitet och förbättrar dess reaktivitet för att uppnå upp till 85% deacetylation på 1-2 timmar. Både [Emim][OAc] och [TBA][OH] kan regenereras (97% respektive 83%), vilket erbjuder en mer hållbar metod för kitosanproduktion som kan tex. fungera som substrat för katalysatorer i industrin. Paper II undersöker adsorption och katalytisk reduktion av fenolröd färgämne med Ag-belastade kitosankatalysatorer. Dessa katalysatorer visar utmärkt aktivitet över ett brett pH-intervall (4–11), med effektiv adsorption vid nästan neutralt pH (6,4) samt vid rumstemperatur. Efter fem återvinningscykler bibehåller katalysatorerna deras strukturella stabilitet med endast 0,2% förlust av Ag, vilket visar deras potential för avloppsvattenrening.

Lignin, en viktig men underutnyttjad polymer i träbiomassa, bränns vanligtvis till energi och värme. Nyligen har intresset ökat för att omvandla lignin till värdefulla produkter som jetbränsle-kolväten och finkemikalier. Utmaningen ligger i att selektivt bryta C–O och C–C-bindningar i lignin samtidigt som katalysatorns stabilitet bibehålls. Paper III undersöker C–O-klyvning i ligninmodelmolekyler med multifunktionella Ru/NbOPO4/TiO2-katalysatorer, vilket ger hög utbyte av kolväten (86,9–100%) under milda betingelser. Paper IV undersöker både C–O och C–C-klyvning med Ru/NbOPO4-katalysatorer, varvid >99% konversion av modellföreningar uppnås med högt utbyte av kolväten. Katalysatorernas prestanda drivs av den justerbara synergismen mellan Lewis- och Brønsted-surheten hos niobiumfosfat och väteaktiveringsrollen hos Ru.

Denna tvärvetenskapliga forskning främjar biopolymerkemi och katalys, och erbjuder hållbara lösningar till miljö- och energimässiga utmaningar genom att maximera användningen av biprodukter från biomassa och tillhandahålla miljövänliga alternativ inom avloppsvattenrening och förnybar energi.

Abstract [vi]

Nghiên cứu này nhằm khám phá tiềm năng của những polymer sinh học có trong các phụ phẩm sinh khối, cụ thể là chitin và lignin, trong việc giải quyết các thách thức về môi trường và năng lượng.

Chitin được tìm thấy nhiều trong vỏ động vật giáp xác và có thể deacetyl hóa để tạo ra chitosan, một vật liệu đa dụng với nhiều ứng dụng trong công nghiệp. Sản xuất chitosan truyền thống thường tiêu tốn nhiều năng lượng và cần đến các tác chất có tính ăn mòn cao. Để cải thiện, Bài báo I giới thiệu một phương pháp ’xanh hơn’, sử dụng chất lỏng ion [Emim][OAc] để xử lý sơ bộ chitin, sau đó tiến hành deacetyl hóa trong dung dịch NaOH hoặc [TBA][OH] với sự hỗ trợ của vi sóng. Quá trình tiền xử lý giúp giảm độ tinh thể của chitin, tăng hoạt tính phản ứng, và đạt tới 85% deacetyl hóa trong 1-2 giờ. Cả [Emim][OAc] và [TBA][OH] đều có thể tái tạo với hiệu suất tương ứng 97% và 83%, đem lại tính bền vững cho phương pháp, và tăng thêm cơ hội cho chitosan trong các ngành công nghiệp, thí dụ như xúc tác. Bài báo II nghiên cứu quá trình hấp phụ và khử thuốc nhuộm phenol đỏ bằng xúc tác Ag/chitosan. Xúc tác này thể hiện hoạt tính cao với phạm vi pH rộng (4–11), và khả năng hấp phụ hiệu quả nhất ở pH gần trung tính (6.4), nhiệt độ phòng. Sau năm lần tái sử dụng, xúc tác vẫn duy trì độ ổn định cấu trúc, mất chỉ 0.2% Ag, chứng minh tiềm năng trong xử lý nước thải.

Lignin là một polymer phổ biến trong sinh khối gỗ, nhưng chưa được khai thác nhiều, mà thường chỉ bị đốt để tạo nhiệt năng. Gần đây, nhiều nghiên cứu bắt đầu tập trung vào việc chuyển hóa lignin thành các sản phẩm có giá trị hơn, như phụ gia nhiên liệu máy bay hay hóa chất thương phẩm. Thách thức nằm ở việc bẻ gãy chọn lọc các liên kết C–O và C–C trong lignin đồng thời duy trì khả năng tái sử dụng của xúc tác. Bài báo III nghiên cứu sự cắt đứt C–O trong các hợp chất mô phỏng lignin bằng xúc tác đa năng Ru/NbOPO4/TiO2. Nghiên cứu cho hiệu suất chuyển hóa cao (86.9–100%), sản xuất hydrocarbon trong điều kiện êm dịu hơn. Bài báo IV nghiên cứu việc cắt đứt đồng thời C–O và C–C với xúc tác Ru/NbOPO4 trong các hợp chất mô phỏng lignin. Chuyển hóa thu được hơn 99% với hiệu suất hydrocarbon cao. Hiệu quả của các xúc tác này liên quan đến sự kết hợp giữa các tâm acid Lewis và Brønsted trong niobium phosphate và sự hoạt hóa hydrogen của Ru.

Nghiên cứu này làm màu mỡ thêm hóa học về polymer và xúc tác, cung cấp thêm các giải pháp bền vững cho các thách thức về môi trường và năng lượng thông qua việc tối đa hóa các phụ phẩm sinh khối trong xử lý nước thải và năng lượng tái tạo.

Place, publisher, year, edition, pages
Umeå: Umeå University, 2025. , p. 70
Keywords [en]
chitin, chitosan, ionic liquid, deacetylation, phenol red dye, lignin, biomass, solid catalyst, biofuels, hydrodeoxygenation, niobium oxyphosphate, titanium dioxide, hydrogenolysis
National Category
Catalytic Processes Polymer Technologies Organic Chemistry Materials Chemistry
Research subject
Organic Chemistry; Materials Science
Identifiers
URN: urn:nbn:se:umu:diva-236300ISBN: 978-91-8070-659-9 (print)ISBN: 978-91-8070-660-5 (electronic)OAI: oai:DiVA.org:umu-236300DiVA, id: diva2:1943288
Public defence
2025-04-04, Lilla Hörsalen, KB.E3.01, Umeå, 09:00 (English)
Opponent
Supervisors
Available from: 2025-03-14 Created: 2025-03-10 Last updated: 2025-03-10Bibliographically approved
List of papers
1. Ionic liquid strategy for chitosan production from chitin and molecular insights
Open this publication in new window or tab >>Ionic liquid strategy for chitosan production from chitin and molecular insights
Show others...
2024 (English)In: RSC Sustainability, E-ISSN 2753-8125, Vol. 2, no 4, p. 1154-1164Article in journal (Refereed) Published
Abstract [en]

To produce chitosan is an interesting research. Chitosan is an important polysaccharide in terms of its various applications in industries and is produced from chitin, an abundant biopolymer in crustacean shell biomass wastes. Traditional processes for chitosan manufacture are commonly based on highly concentrated alkaline or acid solutions which are, however, severely eroding and harmful to the environment. In this study, we have described a ‘greener’ method using 1-ethyl-3-methylimidazolium acetate, [Emim][OAc] ionic liquid (IL), for decrystallization of shrimp crystalline chitin flakes followed by a microwave-mediated NaOH or tetrabutylammonium hydroxide, [TBA][OH], solution-based deacetylation for chitosan production. The decrease in crystallinity in IL pre-treated chitin was confirmed by XRD and SEM analysis which subsequently benefited chitosan production with up to 85% degree of deacetylation (%DDA) in shorter time periods (1-2 hours) and lower alkaline concentrations (20-40%). The %DDA in chitin/chitosan was estimated via FT-IR and NMR analysis. Notably, we could regenerate the ionic liquids: in case of [Emim][OAc] 97 wt.% and in case of [TBA][OH] 83 wt.% could be reused. Roles of ionic liquids in the process were discussed. Molecular dynamics (MD) simulations showed the roles of [TBA]+ cations in the molecular driving forces of [TBA][OH]-induced deacetylation mechanism. The strategy promises a sustainable and milder reaction approach to the existing highly corrosive alkaline- or acid-involved processes for chitosan production.

Place, publisher, year, edition, pages
Royal Society of Medicine Press, 2024
National Category
Chemical Sciences
Research subject
sustainability
Identifiers
urn:nbn:se:umu:diva-222314 (URN)10.1039/d4su00053f (DOI)2-s2.0-85189679118 (Scopus ID)
Available from: 2024-03-13 Created: 2024-03-13 Last updated: 2025-03-10Bibliographically approved
2. Efficient adsorption and catalytic reduction of phenol red dye by glutaraldehyde cross-linked chitosan and its ag-loaded catalysts: materials synthesis, characterization and application
Open this publication in new window or tab >>Efficient adsorption and catalytic reduction of phenol red dye by glutaraldehyde cross-linked chitosan and its ag-loaded catalysts: materials synthesis, characterization and application
Show others...
2023 (English)In: Clean technologies, ISSN 2571-8797, Vol. 5, no 2, p. 466-483Article in journal (Other academic) Published
Abstract [en]

In this study, glutaraldehyde cross-linked chitosan support, as well as the catalysts obtained after loading Ag metal (Ag/Chitosan), were synthesised and applied for adsorption and reduction of phenol red dye in an aqueous solution. The Ag/chitosan catalysts were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis techniques. The catalytic reduction and adsorption performance of phenol red dye with Ag/chitosan and cross-linked chitosan, respectively, was performed at ambient reaction conditions. The reduction of dye was carried out using sodium borohydride (NaBH4) as the reducing agent, while the progress of adsorption and reduction study was monitored with ultraviolet-visible (UV-vis) spectrophotometry technique. The reduction of the phenol red dye varied with the amount of catalyst, the concentration of NaBH4, Ag metal loading, reaction temperature, phenol red dye concentration and initial pH of the dye solution. The dye solution with a nearly-neutral pH (6.4) allowed efficient adsorption of the dye, while acidic (pH = 4) and alkaline (pH = 8, 11, 13.8) solutions showed incomplete or no adsorption of dye. The reusability of the Ag/chitosan catalyst was applied for the complete reduction of the dye, where no significant loss of catalytic activity was observed. Hence, the applicability of cross-linked chitosan and Ag/catalyst was thus proven for both adsorption and reduction of phenol red dye in an aqueous solution and can be applied for industrial wastewater treatment.

Place, publisher, year, edition, pages
MDPI, 2023
Keywords
cross-linked chitosan, Ag/chitosan catalyst, phenol red dye, adsorption, catalytic reduction, catalyst reusability
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-209689 (URN)10.3390/cleantechnol5020024 (DOI)001017001900001 ()2-s2.0-85163765219 (Scopus ID)
Funder
Bio4EnergyKnut and Alice Wallenberg Foundation
Available from: 2023-06-13 Created: 2023-06-13 Last updated: 2025-03-10Bibliographically approved
3. Synergistic catalyst Ru/NbOPO4/TiO2 for selective hydrodeoxygenation of phenolics towards unlocking lignin's potential
Open this publication in new window or tab >>Synergistic catalyst Ru/NbOPO4/TiO2 for selective hydrodeoxygenation of phenolics towards unlocking lignin's potential
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry Chemical Engineering
Identifiers
urn:nbn:se:umu:diva-236298 (URN)
Available from: 2025-03-10 Created: 2025-03-10 Last updated: 2025-03-10Bibliographically approved
4. Precision cleavage of interunit C-C and C-O bonds in lignin biphenyls and its molecular insights
Open this publication in new window or tab >>Precision cleavage of interunit C-C and C-O bonds in lignin biphenyls and its molecular insights
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Engineering Materials Chemistry Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-236299 (URN)
Available from: 2025-03-10 Created: 2025-03-10 Last updated: 2025-03-10Bibliographically approved

Open Access in DiVA

fulltext(4064 kB)79 downloads
File information
File name FULLTEXT01.pdfFile size 4064 kBChecksum SHA-512
ab8a2dff199f31709f098df5620f6b3544d4dcac433d0118545a893fdee077d6a88f3ec7b17820811adf7515fbedf44743796545875176df9fb5afe2d8c3c02a
Type fulltextMimetype application/pdf
spikblad(636 kB)37 downloads
File information
File name SPIKBLAD02.pdfFile size 636 kBChecksum SHA-512
0fb09f126043db531ab03bdccf6696cb9d63342c504adc4d2157215318318489761ec999904806e629c2feaada90b7a251b0cd305846a50c1689fe25f01c3da9
Type spikbladMimetype application/pdf

Authority records

Dinh, Van Minh

Search in DiVA

By author/editor
Dinh, Van Minh
By organisation
Department of Chemistry
Catalytic ProcessesPolymer TechnologiesOrganic ChemistryMaterials Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 79 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 1222 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf